Aminobenzophenones and photopolymerizable compositions including the same

ABSTRACT

Novel benzophenone derivatives and methods of making and using the same are disclosed. The novel compounds can display highly active photoinitiation and photopolymerization properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of pending application Ser.No. 09/368,034, filed Aug. 3, 1999, now U.S. Pat. No. 6,479,706 which isa continuation-in-part application of application Ser. No. 09/017,852,filed Feb. 3, 1998, now abandoned, which is related to commonly ownedProvisional Application Serial No. 60/037,155, filed Feb. 4, 1997. Thisapplication is also related to pending application Ser. No. 08/858,268,filed May 19, 1997, which is related to commonly owned ProvisionalApplication Serial No. 60/017,127, filed May 20, 1996. All of theabove-described applications are incorporated in their entirety byreference.

FIELD OF THE INVENTION

This invention relates generally to novel photoactive compounds andmethods for using the same. More particularly, this invention relates toaminobenzophenones and methods of using the same in photoactivatablepolymerization systems.

BACKGROUND OF THE INVENTION

Ethylenically unsaturated compounds, and in particular acrylatederivatives, can be polymerized by irradiation with ultraviolet light ofwavelength between 200 and 450 nanometers (nm) in the presence of abimolecular photoinitiating system. The photoinitiating system caninclude, for example, (1) a benzophenone derivative and (2) acoinitiator or synergist, that is, a molecule which serves as a hydrogenatom donor. The coinitiators or synergists are typically alcohols,tertiary amines or ethers which have available hydrogens attached to acarbon adjacent to a heteroatom.

One commercially available benzophenone derivative useful as aphotoinitiator is 4,4′-bis(dimethylamino)benzophenone, also referred toin the art as “Michler's Ketone”. Michler's Ketone has the followingstructure:

While Michler's Ketone can be useful as a photoinitiator in radiationcuring of polymers, it is typically used little in the industry due toits potentially hazardous characteristics.

4,4′-Bis(diethylamino)benzophenone (also referred to as tetraethylMichler's Ketone) has been proposed as a possible alternative toMichler's Ketone due to its lower toxicity. However, this compound doesnot exhibit good photoinitiating activity and thus has not been widelyadopted as an alternative to Michler's Ketone.

Other Michler's Ketone derivatives are described, for example, in U.S.Pat. No. 4,507,497 to Reilly, Jr., which is directed to water solubleMichler's Ketone analogs which include amino groups substituted byR¹COOH, in which R¹ is an alkylene group having 1 to 8 carbon atoms.

Examples of other commercially available photoinitiators useful inbimolecular photoinitiator systems include benzophenone,2,4-dimethylbenzophenone, isopropylthioxanthone, and2,4-diethylthioxanthone. The UV absorption spectrum for these individualphotoinitiators, however, do not match-up efficiently with the UVemission spectra of the standard commercially available mercury vaporbulbs.

Thus, commercially viable UV curing processes can require a relativelylarge amount of initiator and synergist incorporated into theformulation. This can lead to cured articles which contain high levelsof residual photoinitiator and synergist, which in turn can result indecreased light fastness and lower resistance to oxidative degradation.In addition, the residual photoinitiator and synergist can be extractedor leach out of the cured article or migrate to the surface of thearticle. Many times the physical properties of the article are degradedby the presence of the residual photoinitiator and synergist.

SUMMARY OF THE INVENTION

It is accordingly an object of the present invention to providecompounds which can be used as photoinitiators in photopolymerizationprocesses. It is also an object of the invention to provide compoundswhich exhibit useful photoinitiation activity with minimal or no adversehazardous characteristics. These and other objects of the presentinvention will become apparent from the following general and detaileddescription of the invention.

The objects of the present invention are achieved based on the discoveryof novel compounds useful in photopolymerization systems. The compoundscan display highly active photoinitiation and photopolymerizationproperties with minimal or no adverse hazardous characteristics.Specifically the compounds can be essentially or substantiallynon-mutagenic. As is well known in the art, photoinitiator that is notconsumed in the photopolymerization reaction may be extracted or leachedfrom the cured product. Therefore a non-mutagenic photoinitiator isespecially desirable.

Still further, the compounds can have desirable ultraviolet wavelengthabsorbance, which in turn can provide advantages when using narrowwavelength lamps. In this regard, advantageously the compounds possessUV spectra with significant absorption bands between 250 and 350 nm andin particular between 290 and 325 nm. Accordingly, the compounds can beirradiated with a narrow wavelength band, high pressure fill UV curinglamp known as an excimer lamp with spectral emphasis in the 250 to 350nm range, and in particular with its peak emission wavelength at or near308 nm, as described in U.S. Pat. No. 5,504,391.

Compounds showing a significantly elevated level of reactivity at thesewavelengths can be used in considerably lower amounts. For example, whenthe compounds of the invention are used with an excimer lamp versus amedium pressure mercury lamp, only about one-fourth of the amount ofphotoinitiator can be required to give equivalent cure speeds. Inaddition, when the same concentration of photoinitiator is used withboth an excimer and a medium pressure mercury lamp the excimer lamp canprovide greatly increased cure speeds. Because less photoinitiator isrequired, less residual photoinitiator can remain in the cured articles,thereby minimizing problems associated with leaching or extraction,decreased light fastness and lower resistance to oxidative degradation.

The compounds of the invention have a structure according to Formula (I)below:

each A is independently selected from the group consisting of hydrogen,lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen,sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio,polymerizable moiety, and oligomeric moiety, with the proviso that nomore than three A are the same lower alkyl;

each R is independently selected from the group consisting of hydrogen,lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen,sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio,polymerizable moiety, and oligomeric moiety; and

n is an integer from 1 to 4.

The present invention also provides photopolymerizable compositionswhich include the compounds of Formula (I) above as a component thereof,as well as methods for the manufacture of the compounds of Formula (I)and methods for the use of the compounds of Formula (I) inphotopolymerization systems.

BRIEF DESCRIPTION OF THE DRAWINGS

Some of the features and advantages of the invention having beendescribed, others will become apparent from the detailed descriptionwhich follows, and from the accompanying drawings, in which:

FIG. 1 illustrates the ultraviolet (UV) emission spectrum of an excimerlamp as described in U.S. Pat. No. 5,504,391; and

FIG. 2 illustrates the UV absorption of4,4′-bis(methylethylamino)benzophenone (MEAB).

DETAILED DESCRIPTION OF THE INVENTION

The novel compounds of the invention include compounds according toFormula (I) below:

each A is independently selected from the group consisting of hydrogen,lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen,sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio,polymerizable moiety, and oligomeric moiety, with the proviso that nomore than three A are the same lower alkyl;

each R is independently selected from the group consisting of hydrogen,lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen,sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio,polymerizable moiety, and oligomeric moiety; and

n is an integer from 1 to 4.

As used herein, the term lower alkyl refers to linear or branched C1-C8alkyl, such as but not limited to methyl, ethyl, propyl, isopropyl,n-butyl, t-butyl, and the like, optionally substituted with one or morehalogen, aryl, arylalkyl, alkylaryl, cycloalkyl, alkoxy, heteroatom, andthe like. The term cycloalkyl refers to C3 to C6 cyclic alkyl, such asbut not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,optionally substituted with one or more halogen, aryl, alkyl, arylalkyl,alkylaryl, cycloalkyl, alkoxy, heteroatom, and the like. The termalkanol refers to lower alkyl substituted with one or more hydroxylgroups. The term lower alkoxy refers to lower alkyl substituted with oneor more oxygen atoms, including but not limited to methoxy, ethoxy,propoxy, butoxy, and the like. The term alkylsulfonyl refers to loweralkyl substituted with sulfonyl. The terms trihaloalkyl, trihaloalkoxy,and trihaloalkylthio refer to lower alkyl, lower alkoxy and loweralkylthio, respectively, in which hydrogen atoms on the organic groupare replaced with halogen, preferably fluorine. The term aryl refers toC3 to C10 cyclic aromatic groups such as but not limited to phenyl,naphthyl, and the like, optionally substituted with one or more halogen,alkyl, arylalkyl, alkylaryl, cycloalkyl, alkoxy, heteroatom, and thelike. The term heteroatom refers to oxygen, nitrogen, sulfur orphosphorous.

The term polymerizable moiety refers to ethylenically unsaturatedmoieties known in the art which are capable of reaction with anothercompound (for example by a free radical mechanism), such as but notlimited to, acrylate and methacrylate moieties. For example A can havethe structure —(CH₂)_(n)—OC(O)— CRH═CH₂, wherein n is an integer from 1to 10 and R is H or lower alkyl. Yet another exemplary polymerizablemoiety can be a maleimide moiety

R′ is selected from the group consisting of —(CH₂)_(n)—, wherein n is aninteger from 0 to 10, optionally substituted with one or more heteroatomin the —CH₂— chain; and

each R″ is independently selected from the group consisting of hydrogen,lower alkyl and halogen.

The term oligomeric moiety refers to a moiety including two or moremonomer units (dimer, trimer, etc.) such as but not limited to an C2-C20alkylene or polyalkylene polyol, wherein hydroxy groups of the polyolare optionally alkylated, and preferably an alkylene or polyalkylenepolyol derived from ethylene glycol. Other suitable oligomer moietiesinclude C2-C20 alkylene or polyalkylene moieties end capped withtrihaloalkyl, and optionally substituted with one or more halogen atomsalong the chain, preferably fluorine. Other exemplary oligomericmoieties include C2-C20 alkylene or polyalkylene moieties includingcarbonate groups and end capped with lower alkyl.

In one embodiment of the invention, each A of the compound of Formula(I) is lower alkyl, preferably methyl or ethyl, with the proviso that nomore than three As are the same. In another embodiment of the inventionat least one A is lower alkyl, preferably methyl or ethyl, and at leastone other A is a polymerizable moiety or an oligomeric moiety.

Exemplary compounds in accordance with Formula I include withoutlimitation:

4,4′-bis(methylethylamino)benzophenone.

wherein x is an integer from 1 to 20; and the like.

Advantageously the compounds of the invention, such as MEAB, areappropriately substituted to possess UV spectra with significantabsorption bands between 250 and 350 nanometers (nm), more preferablybetween 290 and 325 nm, and most preferably about 308 nm.

In another embodiment of the invention, photopolymerizable compositionsare provided which include a compound of Formula (I) above as aphotoinitiator. As used herein, and as will be appreciated by theskilled artisan, the term photopolymerizable composition refers tocompositions which harden or cure upon exposure to radiation.

Generally the compositions of the invention include ethylenicallyunsaturated compounds, including monomers, oligomers, polymers,prepolymers, resinous materials, optionally dispersed or dissolved in asuitable solvent that is copolymerizable therewith, and mixturesthereof, which are photopolymerizable when exposed to a source ofultraviolet (“UV”) radiation. As will be appreciated by the skilledartisan, the photopolymerizable compounds can be monofunctional, or caninclude two or more terminal polymerizable ethylenically unsaturatedgroupings per molecule.

Exemplary photopolymerizable compounds or precursors include, but arenot limited to, reactive vinyl monomers, including acrylic monomers,such as acrylic and methacrylic acids, and their amides, esters, saltsand corresponding nitriles. Suitable vinyl monomers include, but are notlimited to, methyl acrylate, ethyl acrylate, n- or tert-butylacrylate,isooctyl acrylate, methyl methacrylate, ethylmethacrylate, 2-ethylhexylmethacrylate, butylacrylate, isobutyl methacrylate, the correspondinghydroxy acrylates, i.e., hydroxy ethylacrylate, hydroxy propylacrylate,hydroxy ethylhexyl methacrylate, glycol acrylates, i.e., ethylene glycoldimethacrylate, hexamethylene glycol dimethacrylate, the allylacrylates, i.e., allyl methacrylate, diallyl methacrylate, the epoxyacrylates, i.e., glycidyl methacrylate, and the aminoplast acrylates,i.e., melamine acrylate. Others such as vinyl acetate, vinyl andvinylidene halides and amides, i.e., methacrylamide, acrylamide,diacetone acrylamide, butadiene, styrene, vinyl toluene, and the likeare also included. Prepolymers include acrylated epoxides, polyestersand polyurethanes, and are typically combined with a suitable monomerfor viscosity control. The photopolymerizable compounds may bepolymerized to form homopolymers or copolymerized with various othermonomers.

The photopolymerizable compound can be present in the compositions ofthe invention in amounts between about 99.8 and about 90 percent byweight of the composition, preferably between about 99.5 and about 95percent by weight.

In this aspect of the invention, the compounds of Formula (I) act asphotopolymerization initiators. The compounds of Formula (I) are addedto the photopolymerizable compound in an amount sufficient to initiatepolymerization thereof upon exposure to ultraviolet radiation.Preferably the compounds of Formula (I) are present in thephotopolymerizable composition an amount between about 0.2 and 10 partsby weight of the composition, and more preferably between about 0.5 andabout 5 parts by weight, depending on the specific application.

The use of the compounds of Formula (I) can exhibit photoinitiationactivity similar to that of Michler's Ketone, but unexpectedly also havegreatly reduced toxicity.

The compositions of the invention can also include any of the variouspigments, organic and inorganic, known in the art. Exemplary pigmentsinclude, but are not limited to, opacifying pigments such as zinc oxide,titania, e.g., anatase and rutile; basic lead sulfate, magnesiumsilicate, silica, clays, wollastonite, talcs, mica, chromates, ironpigments, wood fluor, microballons, hard polymer particles, glass fiberor flake. Pigments can be present in the compositions of the inventionin conventional amounts, i.e., between about 1 and about 40 percent byweight.

It can also be advantageous to also include as a component of thecompositions of the invention a coinitiator or synergist, that is, amolecule which serves as a hydrogen atom donor. Coinitiators orsynergists are known in the art, and are typically alcohols, tertiaryamines or ethers which have available hydrogens attached to a carbonadjacent to a heteroatom. Such co-initiators are typically present in anamount between about 0.2 and about 25 percent by weight. Suitablecompounds include triethanolamine, methyl-diethanolamine,ethyldiethanolamine and esters of dimethylamino benzoic acid. Thesecompounds behave as co-initiators or accelerators for the primaryphotoinitiators and can increase the efficiency and speed of thepolymerization process.

In addition, the compositions of the present invention may containpolymerization inhibitors, fillers, ultraviolet absorbers and organicperoxides.

The compositions of the invention can be applied or deposited to asurface of a substrate using conventional techniques and apparatus. Thecomposition can be applied as a substantially continuous film;alternatively, the composition can be applied in a discontinuouspattern. Usually the compositions of the invention are fluid at ordinaryoperating temperatures (between ambient and up to about 60° C.).

The thickness of the deposited composition can vary, depending upon thedesired thickness of the resultant cured product. Advantageously, thecomposition is applied to the substrate surface in an amount sufficientto provide a cured coating having a thickness between about 1 micron andabout 250 mils.

Typically, the substrate is coated with the uncured photopolymerizablecomposition and passed under an ultraviolet providing light beam by aconveyer moving at predetermined speeds. The substrate to be coated canbe, for example, metal, mineral, glass, paper, plastic, fabric, ceramic,and the like.

The active energy beams used in accordance with the present inventionmay be ultraviolet light or may contain in their spectra both visibleand ultraviolet light. The polymerization may be activated byirradiating the composition with ultraviolet light using any of thetechniques known in the art for providing ultraviolet radiation, i.e.,in the range of 240 nm and 420 nm ultraviolet radiation. The radiationmay be natural or artificial, monochromatic or polychromatic, incoherentor coherent and should be sufficiently intense to activate thephotoinitiators of the invention and thus the polymerization.Conventional radiation sources include fluorescent lamps, mercury, metaladditive and arc lamps. Coherent light sources are the pulsed nitrogen,xenon, argon ion- and ionized neon lasers whose emissions fall within oroverlap the ultraviolet or visible absorption bands of the compounds ofthe invention. In one embodiment of the invention, the compositionincluding the compounds of the invention is exposed to ultravioletradiation having a wavelength of about 240 to about 420 nm.

As noted above, advantageously the compounds of the invention areappropriately substituted to possess UV spectra with significantabsorption bands between 250 and 350 nm and in particular between 290and 325 nm. Accordingly, the compounds can be irradiated with a narrowwavelength band, high pressure fill UV curing lamp known as an excimerlamp with spectral emphasis in the 250 to 350 nm range, and inparticular with its peak emission wavelength at or near 308 nm, asdescribed in U.S. Pat. No. 5,504,391, the entire disclosure of which ishereby incorporated in its entirety. The compounds of Formula (I) show asignificantly elevated level of reactivity at these wavelengths. Becauseof the increased level of activity the photoinitiator can be used inconsiderably lower amounts. For example, when the compounds of theinvention are used with an excimer lamp versus a medium pressure mercurylamp, only about one-fourth of the amount of photoinitiator can berequired to give equivalent cure speeds. IN addition, when the sameconcentration of photoinitiator is used with both an excimer and amedium pressure mercury lamp the excimer lamp can provide greatlyincreased cure speeds. UV Spectra are provided for the excimer lamp andfor MEAB in FIGS. 1 and 2, respectively.

When polymerized by exposure to UV radiation, the compositions of theinvention give a substantially tack-free product which is durable forordinary handling. The compositions of the invention are useful in anyof the types of applications known in the art for photopolymerizations,including as a binder for solids to yield a cured product in the natureof a paint, varnish, enamel, lacquer, stain or ink. The compositions areparticularly useful in the production of photopolymerizable surfacecoatings in printing processes, such as lithographic printing, screenprinting, and the like.

The compounds of the invention can be prepared from an aniline compoundwhich may be substituted at any position except the 4 position. Thenitrogen atom of the aniline can be substituted using techniques knownin the art. For example, the aniline can be alkylated using knowntechniques. In this regard, the aniline can be converted to anN-ethylaniline by reductive alkylation with acetaldehyde by methodsreviewed by Rylander in “Catalytic Hydrogenation over Platinum Metals.”The N-ethylaniline may be converted to an N-ethyl, N-methylaniline bysubsequent reductive alkylation with formaldehyde. These N-alkylationsmay also be performed with alcohol reagents by methods known in the art.The order of the N-alkylations may also be reversed in order to firstlyform the N-methyl and secondly form the N-ethyl, N-methyl intermediate.The N-ethyl, N-methylaniline may be converted to the4,4′-bis(methylethylamino)benzophenone by reaction with phosgene in themethod of Michler disclosed in Chemische Berichte in the year 1876, p.1914. This synthesis is described in detail in the following example ofthe conversion of N-ethylaniline, which is commercially available fromFirst Chemical Corporation, to the photoinitiator4,4′-bis(methylethylamino)benzophenone.

Alternative synthetic routes are disclosed in Japanese Kokai 08-12630published Jan. 16, 1996 and in German patent 2226039, which teach theformation of a diphenylmethane and subsequent oxidation to form thebenzophenone. For example, to prepare MEAB, N-ethylaniline can bereacted with formaldehyde with palladium catalyst to produceN-ethylmethyl aniline, which can be reacted with formaldehyde to give4,4′-bis(ethylmethylamino)diphenyl methane, which is oxidized using asuitable oxidizing agent, such as chloranil/sodium chlorite. Yet anotheralternative route is amination of 4,4′-bis(chloro)benzophenone withmethylethylamine by the method disclosed in U.S. Pat. No. 2,231,067.

The nitrogen atoms can alternatively be hydroxylated as known in theart, or one can start with hydroxy substituted aniline compounds, suchas N-alkyl,N′-hydroxyalkyl anilines, commercially available, forexample, from First Chemical Corporation. The hydroxyl functionality isreacted with suitable reagents as known in the art to provide thedesired functionality. For example, a hydroxyl functionality can bereacted with a sulfonyl halide to provide sulfonyl groups. A hydroxylfunctionality can alternatively be reacted with acryloyl halide toprovide an acrylate group.

In yet another embodiment of the invention, compounds having at leastone maleimide unit can be prepared according to techniques known in theart. For example, a suitably attached aromatic amine can be reacted withmaleic anhydride (or a substituted maleic anhydride such as citraconicanhydride) in a polar solvent to provide the amic acid. This is followedby an acid catalyzed ring closure to form the imide. Compounds havingmaleimide functional groups are described in pending U.S. provisionalapplication Serial No. 60/047,729; pending U.S. application Ser. No.08/917,024; Z. Y. Wang, Synthetic Comm. 20(11) 1607-1610 (1990); P. O.Tawnet et al., J.Org.Chem. 26, 15 (1961); and U.S. Pat. No. 2,542,145,the entire disclosure of each of which is hereby incorporated byreference. See also U.S. Pat. Nos. 5,629,356 and 5,468,904 and WO96/33156, the entire disclosure of each of which is also incorporated byreference, which are directed to compounds which have polymerizable oroligomeric moieties incorporated therein.

Other compounds which can be converted to a benzophenone include, butare not limited to, N-ethyl-m-toluidine, o-toluidine, m-toluidine,3-propylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline,2,6-dimethylaniline, 3,5-dimethylaniline, 2-cyclopentylaniline,o-anisidine, m-anisidine, 2-(methylsulfonyl)aniline, 2-fluoroaniline,2-chloroaniline, 3-chloroaniline, 2,6-dichloroaniline,2,3,5,6-tetrachloroaniline, 2-(trifluoromethyl)aniline,3-(trifluoromethyl)aniline, 2-(trifluoromethoxy)aniline,2-[(trifluoromethyl)thio]aniline, and the like.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 Synthesis of 4,4′-Bis(methylethylamino)benzophenone (MEAB)

Ethyl-aniline is methylated by reductive alkylation with formaldehydeusing isopropyl alcohol as a solvent at 100° C. under 120 psi of H₂.After the solvent is stripped the product ethylmethylaniline (NEMA) ispurified by distillation at 120° C. at a pressure of 21 mm mercury (Hg).NEMA (80 g, 0.59 mol) is charged to a vessel fitted with a dry-icecondenser and is heated to 50-60° C. Phosgene is transferred from acylinder to a calibrated trap placed in dry-ice. After condensing 10 mL(14.3 g, 0.145 mol), the trap was connected to the vessel containingNEMA and the phosgene was added over 1 hour. After the addition wascomplete, the mixture was heated to 120° C. and held at this temperaturefor 1 hour. The mixture was cooled to 50-60° C. before 11 g (0.275 mol)of NaOH dissolved in 100 mL of water was added to hydrolyze theunreacted acid chloride. The resulting mixture was then extracted withtwo 100 mL portions of toluene. The product4,4′-bis(methylethylamino)benzophenone (MEAB) was purified bychromatography on silica gel using toluene as an eluent followed byrecrystallization from methylene chloride/hexane. Several grams ofhighly pure MEAB were obtained. No impurities were detectable by NMR;m.p. 122-124° C. NMR, IR and mass spectra were consistent with theproposed structure.

EXAMPLE 2 Use of MEAB as Photoinitiator

Michler's Ketone (also tetramethyl Michler's Ketone or TMMK), tetraethylMichler's Ketone (also 4,4′-bis(diethylamino)benzophenone or TEMK), andMEAB were tested in curing hexanediol diacrylate compositions. Thecomposition included 1% isopropylthioxanthone, 2% ethyl4-N,N-dimethylaminobenzoate, 4% benzophenone, 1% aminobenzophenonecompound, and the balance hexanediol diacrylate. The composition wasapplied as a 0.15 inch film to a substrate and cured with a Fusion UVSystems “H” bulb with 600 Watts/inch power with a belt speed of 55 feetper minute. MEAB and TMMK both required 10 passes under the lamp toobtain a well-cured hard polymer, and TEMK required 25 passes. Thisillustrates that MEAB and TMMK have approximately the same activity, andboth are much superior to the tetraethyl compound.

EXAMPLE 3 Comparative Mutagenicity of TMMK, TEMK and MEAB

Michler's ketone (TMMK) is listed by the National Toxicology Program as“reasonably anticipated to be a carcinogen” based on the results ofcancer studies in rats and mice. Seventh Annual Report on Carcinogens,U.S. Dept. Health Human Services, p. 259, 1994. Based on comparisons ofmutagenicity studies with animal cancer studies, mutagens are morelikely to cause cancer, to produce tumors in multiple organs, and toaffect multiple species. Gold, L. S. et al., Mutat. Res. 286, 75-100(1993).

Mutagenicity can be measured by a variety of assays. The most commonlyused method is the Salmonella/Mammalian-Microsome Reverse MutationScreening Assay (Ames Test), which commonly uses four or five strains ofSalmonella bacteria to detect different types of mutations.

Michler's Ketone has been tested in the Ames Test a number times.Scribner, J. D. et al. Cancer Lett. 9, 117-121 (1980); McCarthy, D. J.et al. Mutat. Res. 119, 7-14 (1983); Dunkel, V. C. et al., Environ.Mutagen. 7 (Suppl. 5), 1-248 (1985); Zeiger, E. et al., Environ. Mol.Mutagen. 19 (Suppl. 21), 2-141 (1992). In this assay, the bacterialstrain which was consistently found to have mutations when adequateconcentrations of test material were used was strain Salmonellatyphimurium tester strain TA98, with added mammalian metabolicactivation. Dunkel, V. C. et al., Environ. Mutagen. 7 (Suppl. 5), 1-248(1985); Zeiger, E. et al., Environ. Mol. Mutagen. 19 (Suppl. 21), 2-141(1992).

TMMK, TEMK and MEAB were evaluated for the ability to induce reversemutations at the histidine locus in the genome of a specific Salmonellatyphimurium tester strain in the presence of an exogenous metabolicactivation system of mammalian microsomal enzymes derived fromAroclor™-induced rat liver (S9). The tester strain used in themutagenicity assay was Salmonella typhimurium tester strain TA98 withadded activation. The assay was conducted using eight doses of the testarticle, along with the appropriate vehicle and positive controls in thepresence of S9 mix (S9 homogenate was purchased from MolecularToxicology, Inc., Annapolis, Md. 21401, Batch 0646, 43.4 mg of proteinper ml). Positive controls were also plated in the absence of S9 mix.All doses of test article, vehicle, and positive controls were plated intriplicate.

1. Test Article Handling

The test article TMMK was stored at room temperature. Acetone (CAS#67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle. At20 mg per ml, which was the most concentrated stock solution which couldbe prepared, the test article formed a clear, light yellow solution. Thetest article remained a solution in all succeeding dilutions preparedfor the mutagenicity assay. The maximum aliquot of acetone which can beused in the test system is 200 μl. Thus, the maximum concentration whichcould be tested was 4,000 μg per plate. The test article and vehiclecontrols were plated using a 200 μl plating aliquot. Positive controlarticles were plated using 50 μl plating aliquot.

The test article TEMK was stored at room temperature. Acetone (CAS#67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle. At100 mg per ml, which was the most concentrated stock solution prepared,the test article formed a clear, yellow solution. The test articleremained a solution in all succeeding dilutions prepared for themutagenicity assay. The test article, vehicle controls and positivecontrol articles were plated using a 50 μl plating aliquot.

The test article MEAB was stored at room temperature. Acetone (CAS#67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle. At25 mg per ml, which was the most concentrated stock solution prepared,the test article formed a clear, light yellow solution. The test articleremained a solution in all succeeding dilutions prepared for themutagenicity assay. The test article and vehicle controls were platedusing a 200 μl plating aliquot. Positive control articles were platedusing a 50 μl plating aliquot.

2. Mutagenicity Assay

The mutagenicity assay results for TMMK, TEMK, and MEAB are presented inTable 1. The data are presented as individual plate counts along with amean and standard deviation.

The results of the Salmonella/Mammalian-Microsome Reverse MutationScreening Assay (Ames Test) indicate that TMMK did cause a positive(3.9-fold) increase in the number of revertants per plate with testerstrain TA98 in the presence of S9 mix. Test articles TEMK and MEAB didnot cause a positive increase in the number of revertants per plate withtester strain TA98 in the presence of S9 mix. Of the three testmaterials, only TMMK was mutagenic. For aromatic amino or nitrocompounds such as these test materials, very few which were notmutagenic in the Ames test have been found to cause tumors in animalcancer studies. Ashby, J. and Tennant, R. W., Mutat. Res. 257, 229-306(1991). Therefore, these results suggest that MEAB has a lower potentialto cause tumors than TMMK.

TABLE 1 MUTAGENICITY ASSAY RESULTS INDIVIDUAL PLATE COUNTS REVERTANTSPER PLATE COMPOUND TMMK TEMK MEAB BACK BACK BACK GROUND GROUND GROUNDSAMPLE 1 2 3 LAWN* 1 2 3 LAWN* 1 2 3 LAWN* MICROSOMES Rat Liver 10 22 301 16 36 11 1 9 20 30 1 VEHICLE CONTROL TEST ARTICLE (DOSE/PLATE)  3.33μg 14 29 24 1 22 22 30 1 13 21 22 1   100 μg 9 19 19 1 30 24 20 1 25 2811 1  33.3 μg 21 35 37 1 13 23 19 1 24 25 24 1   100 μg 16 12 22 1 sp 2826 24 1 20 18 20 1 sp   333 μg 18 23 12 1 mp 20 17 19 1 sp 21 31 19 1 mp 1000 μg 35 26 33 1 mp 32 23 17 1 mp 36 23 21 1 mp  3330 μg 78 82 78 6mp 27 15 25 1 mp 27 14 17 1 hp  4000 μg 80 70 93 6 mp NT NT NT — NT NTNT —  5000 μg NT NT NT — 27 19 19 1 mp 23 23 27 1 hp POSITIVE CONTROL**1053 920  932  1 1264 1032 1133 1 1196 1225 1226 1 **TA982-aminoanthracene 2.5 μg/plate *Background Lawn Evaluation Codes: 1 =normal 2 = slightly reduced 3 = moderately reduced 4 = extremely reduced5 = absent 6 = obscured by precipitate sp = slight precipitate mp =moderate precipitate (requires hand count) hp = heavy precipitate(requires hand count) NT = Not tested

TABLE 2 MUTAGENICITY ASSAY RESULTS SUMMARY MEAN REVERTANTS PER PLATEWITH STANDARD DEVIATION COMPOUND TMMK TEMK MEAB DOSE/PLATE BACK- BACK-BACK- GROUND GROUND GROUND MEAN S.D. LAWN* MEAN S.D. LAWN* MEAN S.D.LAWN* MICROSOMES: Rat Liver 21 10 1 21 13 1 20 11 1 VEHICLE CONTROLDOSE/PLATE  3.33 μg 22 8 1 25 5 1 19 5 1  10.0 μg 16 6 1 25 5 1 21 9 1 33.3 μg  31 9 1 18 5 1 24 1 1    100 μg 17 5 1 sp 26 2 1 19 1 1 sp  333 μg 18 6 1 mp 19 2 1 sp 24 6 1 mp  1000 μg  31 5 1 mp 24 8 1 mp 278 1 mp  3330 μg  79 2 6 mp 22 6 1 mp 19 7 1 hp  4000 μg  81 12  6 mp NT— — NT — —  5000 μg  NT — — 22 5 1 mp 24 2 1 hp POSITIVE CONTROL** 968 74  1 1143  116  1 1216  17  1 **TA98 2-aminoanthracene 2.5 μg/plate*Background Lawn Evaluation Codes: 1 = normal 2 = slightly reduced 3 =moderately reduced 4 = extremely reduced 5 = absent 6 = obscured byprecipitate sp = slight precipitate mp = moderate precipitate (requireshand count) hp = heavy precipitate (requires hand count) NT = Nottested.

The foregoing examples are illustrative of the present invention and arenot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

That which is claimed:
 1. A method for making an ink havingsubstantially no mutagenic leachates, comprising exposing a compositioncomprising pigment and a photopolymerizable compound having at least oneethylenically unsaturated double bond to radiation in the presence of asubstantially non-mutagenic photoinitiator having photoinitiationactivity similar to that exhibited by4,4′-bis(dimethylamino)benzophenone under similar conditions, saidphotoinitiator having the formula

each A is independently selected from the group consisting of hydrogen,lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen,sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio,polymerizable moiety —(CH₂)_(n)—OC(O)—CR′H═CH₂ wherein n′ is an integerfrom 1 to 10 and R′ is H or lower alkyl, polymerizable maleimide moiety,and oligomeric moiety, with the proviso that no more than three A arethe same lower alkyl; each R is independently selected from the groupconsisting of hydrogen, lower alkyl, cycloalkyl, aryl, lower alkanol,lower alkoxy, halogen, sulfonyl, alkylsulfonyl, trihaloalkyl,trihaloalkoxy, trihaloalkylthio, polymerizable moiety, and oligomericmoiety; and n is an integer from 1 to
 4. 2. The method of claim 1,wherein each A is independently lower alkyl.
 3. The method of claim 2,wherein two As are methyl and two As are ethyl.
 4. The method of claim2, wherein three As are methyl and one A is ethyl.
 5. The method ofclaim 2, wherein three As are ethyl and one A is methyl.
 6. The methodof claim 1, wherein the photoinitiator is selected from the groupconsisting of 4,4′-bis(methylethylamino)benzophenone,4-(dimethylamino)-4′-(methylethylamino)benzophenone,4-(diethylamino)-4′-(methylethylamino)benzophenone,4,4′-bis(methylethanolamino) benzophenone,4,4′-bis(methylmethylacrylateamino) benzophenone,4,4′-bis(maleimideamino) benzophenone, and4-(methylethylamino)-4′-(aliphatic maleimideamino) benzophenone havingthe formula

wherein x is an integer from 1 to 20, and mixtures thereof.
 7. Themethod of claim 1, wherein each R is hydrogen.
 8. The method of claim 1,wherein the photopolymerizable compound comprises an acrylate.
 9. Themethod of claim 1, wherein the photopolymerizable compound is themajority component of the composition.
 10. The method of claim 1,wherein the photopolymerizable compound is selected from the groupconsisting of methyl acrylate, ethyl acrylate, n-butylacrylate,tert-butylacrylate, isooctyl acrylate, methyl methacrylate,ethylmethacrylate, 2-ethylhexyl methacrylate, butylacrylate, isobutylmethacrylate, corresponding hydroxy acrylates, glycol acrylates, allylacrylates, epoxy acrylates, aminoplast acrylates, vinyl acetate, vinylhalides, vinylidene halides, vinyl amides, vinylidene amides, butadiene,styrene, and vinyl toluene.
 11. The method of claim 1, wherein thephotopolymerizable compound is present in an amount of from about 90.0percent by weight to about 99.8 percent by weight in the composition.12. The method of claim 11, wherein the photopolymerizable compound ispresent in an amount of from about 95.0 percent by weight to about 99.5percent by weight in the composition.
 13. The method of claim 1, whereinthe photoinitiator is present in an amount of from about 0.2 to about 10parts by weight of the composition.
 14. The method of claim 13, whereinthe photoinitiator is present in an amount of from about 0.5 to about 5parts by weight.
 15. The method of claim 1, wherein the pigment isselected from the group consisting of zinc oxide, titania, basic leadsulfate, magnesium silicate, silica, clays, wollastonite, talcs, mica,chromates, iron pigments, wood fluor, microballons, hard polymerparticles, glass fiber and glass flake.
 16. The method of claim 1,wherein the pigment is present in an amount of from about 1 to about 40percent by weight in the composition.
 17. The method of claim 1, whereinthe composition further comprises at least one component selected fromthe group consisting of polymerization inhibitors, fillers, ultravioletabsorbers and organic peroxides.
 18. The method of claim 1, wherein thecomposition further comprises a coinitiator.
 19. The method of claim 18,wherein the coinitiator is selected from the group consisting oftriethanolamine, methyl-diethanolamine, ethyldiethanolamine and estersof dimethylamino benzoic acid.
 20. The method of claim 18, wherein thecoinitiator is present in an amount of from about 0.2 to about 25percent by weight of the composition.
 21. The method of claim 1, whereinsaid exposing step comprises exposing the composition to radiationhaving a wavelength of about 250 to about 350 nanometers (nm).
 22. Themethod of claim 1, wherein said exposing step comprises exposing thecomposition to radiation having a wavelength of about 290 to about 325nm.
 23. The method of claim 1, wherein said exposing step comprisesexposing the composition to radiation having a wavelength of about 308nm.
 24. A method for making an ink having substantially no mutagenicleachates and substantially free of epoxy resin, comprising exposing acomposition comprising pigment and a photopolymerizable acrylatecompound having at least one ethylenically unsaturated double bond toradiation in the presence of a substantially non-mutagenicphotoinitiator having photoinitiation activity similar to that exhibitedby 4,4′-bis(dimethylamino)benzophenone under similar conditions, saidphotoinitiator selected from the group consisting of4,4′-bis(methylethylamino)benzophenone,4-(dimethylamino)-4′-(methylethylamino)benzophenone,4-(diethylamino)-4′-(methylethylamino)benzophenone,4,4′-bis(methylethanolamino) benzophenone,4,4′-bis(methylmethylacrylateamino) benzophenone,4,4′-bis(maleimideamino) benzophenone, and4-(methylethylamino)-4′-(aliphatic maleimideamino) benzophenone havingthe formula

wherein x is an integer from 1 to 20, and mixtures thereof.
 25. Themethod of claim 24, wherein the photoinitiator is4,4′-bis(methylethylamino)benzophenone.
 26. The method of claim 24,wherein the photopolymerizable acrylate compound is selected from thegroup consisting of methyl acrylate, ethyl acrylate, n-butylacrylate,tert-butylacrylate, isooctyl acrylate, methyl methacrylate,ethylmethacrylate, 2-ethylhexyl methacrylate, butylacrylate, isobutylmethacrylate, corresponding hydroxy acrylates, glycol acrylates, allylacrylates, epoxy acrylates and aminoplast acrylates.
 27. The method ofclaim 24, wherein the photopolymerizable compound is present in anamount of from about 90.0 percent by weight to about 99.8 percent byweight in the composition.
 28. The method of claim 27, wherein thephotopolymerizable compound is present in an amount of from about 95.0percent by weight to about 99.5 percent by weight in the composition.29. The method of claim 24, wherein the photoinitiator is present in anamount of from about 0.2 to about 10 parts by weight of the composition.30. The method of claim 29, wherein the photoinitiator is present in anamount of from about 0.5 to about 5 parts by weight.
 31. The method ofclaim 24, wherein the pigment is selected from the group consisting ofzinc oxide, titania, basic lead sulfate, magnesium silicate, silica,clays, wollastonite, talcs, mica, chromates, iron pigments, wood fluor,microballons, hard polymer particles, glass fiber and glass flake. 32.The method of claim 24, wherein the pigment is present in an amount offrom about 1 to about 40 percent by weight in the composition.
 33. Themethod of claim 24, wherein the composition further comprises at leastone component selected from the group consisting of polymerizationinhibitors, fillers, ultraviolet absorbers and organic peroxides. 34.The method of claim 24, wherein the composition further comprises acoinitiator.
 35. The method of claim 34, wherein the coinitiator isselected from the group consisting of triethanolamine,methyl-diethanolamine, ethyldiethanolamine and esters of dimethylaminobenzoic acid.
 36. The method of claim 34, wherein the coinitiator ispresent in an amount of from about 0.2 to about 25 percent by weight ofthe composition.
 37. The method of claim 24, wherein said exposing stepcomprises exposing the composition to radiation having a wavelength ofabout 250 to about 350 nanometers (nm).
 38. The method of claim 24,wherein said exposing step comprises exposing the composition toradiation having a wavelength of about 290 to about 325 nm.
 39. Themethod of claim 24, wherein said exposing step comprises exposing thecomposition to radiation having a wavelength of about 308 nm.